CN101155873A - Polyester composition with high dimensional stability - Google Patents
Polyester composition with high dimensional stability Download PDFInfo
- Publication number
- CN101155873A CN101155873A CNA2005800489712A CN200580048971A CN101155873A CN 101155873 A CN101155873 A CN 101155873A CN A2005800489712 A CNA2005800489712 A CN A2005800489712A CN 200580048971 A CN200580048971 A CN 200580048971A CN 101155873 A CN101155873 A CN 101155873A
- Authority
- CN
- China
- Prior art keywords
- polyester
- mica
- weight
- resin composition
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/251—Mica
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
The present invention relates to thermoplastic compositions having; high dimensional stability at high temperatures. In particular it is directed to polyester compositions containing mica for use in dual-ovenable trays and clear lids for hot food containers. According to one embodiment, the present invention is directed to a polyester composition comprising a polyester containing greater than about 2 to less than about 10 weight % of a mica filler. According to another embodiment of the present invention the mica containing polyester is prepared by the addition of the mica during polymerization, using a buffer to minimize diethylene glycol formation. According to another embodiment of the present invention, the polyester composition containing greater than 2 to less than 10 weight % mica also contains an additive package of impact modifier, nucleating agent and pigment in a concentration from about 5 weight % to 20 weight of the total composition. According to another embodiment of the present invention, the polyester composition containing mica is thermoformed into a container, such as a food tray.
Description
Background of invention
1) invention field
The thermoplastic polyester composition that has high-dimensional stability when the present invention relates to high temperature.Especially, but its relate to the foodstuff container dish that is used for dual-heated and that be used for heat a transparent cover contain the micaceous polymer blend.Said composition contains greater than 2 weight % but usually less than the mica of about 10 weight %.And the micaceous particle diameter is in the about 300 microns scope of about 10-, and it has the long-width ratio greater than about 10.In addition, composition randomly contains the sodium acetate for the about 0.2 weight % of about 0.05-of composition as buffer reagent.In the beginning of transesterify or when transesterify finishes mica is incorporated in the technology for preparing polyester.
2) prior art
The engineering plastics field is well known that uses filler to improve the physicals of molded parts.Filler has improved tensile strength, hardness, shock resistance, toughness, thermotolerance, has reduced creep and mould shrinkage.Usually filler uses with the load of the 20-60 weight % of plastics.Typical filler is glass fibre, carbon/graphite fibre, grind mica, talcum, clay, lime carbonate and other mineral compound of metal oxide for example.
The U.S. Patent No. 3,764,456 of Woodhams discloses to be used to the long-width ratio of the 10-70 volume % of matrix material greater than 30 mica to improve the modulus and the intensity of matrix material.
The U.S. Patent No. 4,257,929 of Borman discloses with mica enhanced polybutylene terephthalate (PBT) resin that is coated with poly-(tetrafluoroethylene) resin.The preferred amounts of the filler that applies is 15 to 45 weight parts of total composition.Observe the improvement of shock strength, heat-drawn wire and flexural strength.
The particle diameter that the U.S. Patent No. 4,536,425 of Hekal discloses by preferred use 30-50 weight % has the method for the resin of improved gas permeability greater than 100 microns mica preparation, wherein when melting mixing with mica splitting to improve its long-width ratio.
The U.S. Patent No. 4,693,941 of Ostapenchenko discloses and has contained the small amount of ethylene trimer and be at least 10 mineral material enhanced polyethylene terephthalate (PET) composition with long-width ratio.The consumption of reinforcing filler is 10-50 weight %, and composite mold is made the articles thermoformed therefrom that is used for automobile.
The U.S. Patent No. 4,874,809 of Keep discloses the polymer blend with low thermal distortion that is used for injection molded article.Said composition is polyester, poly-(terephthalic acid cyclohexanedimethanoester ester) and glass fibre and micaceous mixture.The amount of reinforcing filler is 10 to 25 weight % of total composition.
The U.S. Patent No. 5,300,747 of Simon discloses the matrix material that is used for microwave oven, and it comprises specific inductivity is that 5-8, particle diameter are the particulate state dielectric substance of 1-10 micron.The micaceous consumption for example is the load of 25 weight.
The Japanese Patent Application Publication 63-148030 of Hori etc. relates to and contains mean diameter is but that 10-300 micron, mean aspect ratio are the micaceous PET heat food dish of the 10-45 weight % of 10-45.Mica is used to improve the thermotolerance of thermoforming PET dish, eliminates the big and thick stain that takes place when thermoforming, and the gas of improvement dish (steam) barrier.Hori can not address these problems when having instructed mica to be lower than 10 weight %.Preferred range is the mica of 20-40 weight %.
The Japanese Patent Application Publication 2003-292 748 of Keiichi discloses the application that mica particles is used to reduce the gas permeability of PET bottle.The micaceous consumption is 0.5-2 weight %, and higher load produces opaque bottle.
The U.S. Patent No. 5,342,401 of Dalgewicz etc. discloses the moldable polyester composition that is used for improved barrier properties for gases of having of container and low thermal shrinkage behavior.This realizes by control heating and cooling in hot-forming die.
The U.S. Patent No. 5,344,912 and 6,169,143 of Dalgewicz etc. discloses the polymer blend that comprises impact modifying agent with improved impact property, oxygen perviousness and dimensional stability.But the container that is used for dual-heated by the goods of said composition preparation.
The U.S. Patent No. 6,576,309 of Dalgewicz etc. discloses the polymer blend with improved mould performance, high size and temperature stability.This realizes by ethylene acrylate copolymer is blended in the polyester with optional compatilizer/emulsifier/surfactant.But these compositions are as the container of dual-heated.Dalgewicz does not provide example, but reaffirms that his described hot formed dish is insufficient aspect high-temperature stability.
Therefore but exist demand to the polymer blend of being strict with most of the container that can satisfy dual-heated.But dual-heated means food and can heat in microwave or conventional oven.Also exist demand, for example be used to cook the lid of poultry the lid that is used for hot foodstuff container with better thermal dimensional stability.Also exist demand to these goods with improved oxygen-barrier property.
Summary of the invention
According to an embodiment, the present invention relates to contain the polymer blend of polyester, it contains greater than 2 but less than the mica filler of 10 weight %.
According to another implementation of the invention, when polymerization, add mica and prepare and contain the micaceous polyester, use buffer reagent to make that the formation of glycol ether minimizes in the polyester.
According to another implementation of the invention, contain greater than 2 but also contain the additive-package of impact modifying agent, nucleator and pigment less than the micaceous polymer blend of 10 weight %, its concentration is about 5 weight %-20 weight % of total composition.
According to further embodiment of the present invention, will contain the micaceous polymer blend and be thermoformed into for example container of food tray.
The detailed description of preferred implementation
Opposite with the instruction of prior art, the mica of having found to add low-level (greater than 2 but less than 10 weight %) can significantly improve the thermal dimensional stability of polyester article.A possible explanation is to exist functional group's (season amino) or remaining hydroxyl in the mica, and it can influence the chemical reaction of polyester on the interface.
Usually, polyester or copolyesters can be by a kind of preparations the in following two kinds of methods, that is: (1) ester method and (2) sour method.The ester method be wherein at least one dicarboxyl ester (dimethyl terephthalate (DMT) for example DMT) is reacted in transesterification reaction with at least one glycol (for example ethylene glycol (EG)).Because reaction is a reversible, need remove alcohol (is methyl alcohol) usually when using dimethyl terephthalate (DMT) up hill and dale feedstock conversion is become monomer.So the monomer of preparation contains the short chain oligomer and the mixture of a spot of starting raw material sometimes.Known some catalyzer is used for transesterification reaction.In the past, for example introducing when transesterification reaction finishes, the phosphorus compound of Tripyrophosphoric acid comes hidden activity of such catalysts.Hidden transesterification catalyst mainly is to prevent the polymkeric substance flavescence.
Monomer carries out polycondensation then, and the catalyzer that uses in this reaction is antimony, germanium or titanium compound normally, or the mixture of these compounds or other similar known metal compounds.
In second method of preparation polyester or copolyesters, at least one dicarboxylic acid (for example terephthalic acid) reacts by direct esterification with at least one glycol (for example ethylene glycol) and produces monomer and water.So the monomer of preparation contains the short chain oligomer and the mixture of a spot of starting raw material sometimes.This reaction and ester method are similar also to be reversible, therefore need remove water and finish to order about reaction.In most of the cases direct esterification step does not need catalyzer.As described in the ester method, monomer carries out polycondensation then forming polyester, the catalyzer of use and condition usually with the ester method in used identical.
Suitable polyester is by the prepared in reaction of diacid or diester component and diol component, and wherein diacid or diester component contain terephthalic acid or the C of at least 65 moles of % in the acid moieties in the product
1-C
4The dialkyl group terephthalate, preferably at least 70 moles of %, more preferably at least 80 moles of % even more preferably at least 90 moles of %, wherein diol component contains ethylene glycol or the C of at least 65 moles of % in the glycol moiety in the product
2-C
20Glycol ether (diglycol), preferably at least 70 moles of %, more preferably at least 80 moles of % even more preferably at least 95 moles of %.Also the preferred diacids component is a terephthalic acid, and diol component is an ethylene glycol, therefore forms polyethylene terephthalate (PET).The molar percentage of all diacid component adds up to 100 moles of %, and the molar percentage of all diol components adds up to 100 moles of %.
When polyester components is used one or more diol component modifications except ethylene glycol, the suitable diol component of above-mentioned polyester can be selected from 1,4-cyclohexanedimethanol, 1,2-propylene glycol, 1,4-butyleneglycol, 2,2-dimethyl-1, ammediol, 2-methyl isophthalic acid, ammediol (2MPDO), 1,6-hexylene glycol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol and in chain, contain the glycol of one or more Sauerstoffatoms, for example glycol ether, triethylene glycol, dipropylene glycol, tripropylene glycol or its mixture etc.Usually, these glycol contain 2-18, preferred 2-8 carbon atom.Can use the cycloaliphatic glycol of the mixture of cis or trans structure or these two kinds of forms.Preferred modification diol component is 1,4 cyclohexane dimethanol or glycol ether or its mixture.
When polyester components is used one or more acid constituents modifications except terephthalic acid, the suitable acid constituents (aliphatics, alicyclic or aromatic dicarboxylic acid) of the linear polyester that generates can be selected from for example m-phthalic acid, 1,4-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, succsinic acid, pentanedioic acid, hexanodioic acid, sebacic acid, 1,12-dodecanedioic acid, 2,6-naphthalene dicarboxylic acids, diphenic acid, trimellitic acid or its mixture etc.In polymer manufacture, often preferred its functionality acid derivative, for example dimethyl of dicarboxylic acid, diethyl or the dipropyl used.If feasible, also can use these sour acid anhydrides or sour halogenide.Compare with terephthalic acid, these sour properties-correcting agent have postponed crystallization rate usually.The multipolymer of PET and m-phthalic acid most preferably.Usually the amount of m-phthalic acid is the about 10 moles of % of about 0.5-of multipolymer, preferably about 1.0-7 mole %.
Except polyester or above-mentioned modified poly ester by terephthalic acid (or dimethyl terephthalate (DMT)) and ethylene glycol, the present invention also comprise use 100% for example 2, the aromatic diacid of 6-naphthalene dicarboxylic acids or diphenic acid or its diester, and by at least 85 moles of % from the dicarboxylic ester of these aromatic diacid/diester and the modified poly ester of any prepared in reaction in the above-mentioned comonomer.
Be used for polyester of the present invention and preferably have greater than 0.6, the limiting viscosity (IV) more preferably greater than 0.75.Higher molecular weight is given the higher intensity of goods of gained.
Can be by obtain the polyester of higher IV by the solid state polymerization (SSP) that hangs down the IV polyester of melt polymerization process.By the amorphous of standard melt polymerization process preparation and or a kind of in the many known method in this area of partial crystallization sheet in be solid state polymerization, for example in vacuum tumbler moisture eliminator in batches by rotating heating or in the presence of rare gas element, improving molecular weight by post continuously.
Used mica is not limited to any specific type among the present invention.Can use white mica, phlogopite, biotite, paragonite or synthetic mica.Also can use the mica of surface treatment (silane, titanic acid ester or amino).Preferred wet lapping white mica.
Be used for mean cloud master batch of the present invention and directly be about 300 microns of about 10-(μ m), the about 150 μ m of preferably about 10-, the more preferably from about about 100 μ m of 10-.Demonstrate insufficient thermal dimensional stability by containing the molded goods of micaceous polyester of particle diameter less than about 10 μ m.Poor by containing particle diameter greater than the molded products appearance of the micaceous polyester of about 300 μ m, and contain the hole that in molding process, produces.
Requirement is used for micaceous long-width ratio of the present invention greater than about 10, preferably is higher than approximately 25, most preferably is higher than about 50.Long-width ratio does not have the upper limit, but is lower than at about 10 o'clock, demonstrates insufficient thermal dimensional stability by the molded goods of this polymer blend.
Be used for the 2 weight %s of micaceous amount of the present invention, but be lower than 10 weight % greater than polymer blend.When being lower than about 2 weight %, molded goods demonstrate insufficient thermostability, and when being higher than about 10 weight %, the fragility of molded goods improves.
Preferably with concentration in ethylene glycol the pulp of mica with 30-40 weight %.This slurry is added when esterif iotacation step begins or finish.For preventing the increase of glycol ether in the polyester (DEG), can use for example buffer reagent of sodium acetate, be preferably the about 0.2 weight % of about 0.05-of the initial charge of raw material.
Although can in molding process, prepare the micaceous masterbatch that contains about at the most 30 weight %, find that the mica that adds aequum when in polymerization can obtain good performance by being reduced to desired level.
But for the dual-heated dish, to add softening agent, nucleator, impact modifying agent, releasing agent, stablizer or tinting material with the performance of the thermoforming process of improvement dish or formation without any restriction.To use silane coupling agent or various types of dispersion agent with improve mica to micaceous dispersiveness between the combination of polyester matrix or polymerization period also without any qualification.For transparent foodstuff container, as long as its not remarkably influenced transparency also can be used these additives.
But the typical additive bag of dual-heated dish is disclosed in United States Patent (USP) 5,409,967 and 6,576,309, and it is incorporated herein by reference at this.
The foodstuff container that for example coils and cover and so on prepares by thermo shaping method usually, yet also can use injection moulding and compression moulding.In thermo shaping method,, the fused polymkeric substance is extruded into sheet material and on cylinder, cools off polymer blend fusion and mix in forcing machine.Thermoforming is also referred to as vacuum forming, is the thermoplastic sheet heating is easily stretched until its softness, uses mechanical force and vacuum to force the profile of the sheet material of heat near mould then.After the shape of keeping mould by normal atmosphere and cooling, plastics sheet has kept the shape and the details of mould.Goods are being higher than 100 ℃, preferably are being higher than that annealing can obtain improved thermotolerance under 130 ℃ the temperature in mould.For transparent article, importantly with the temperature optimization of time and mould obtaining maximum degree of crystallinity, and the fuzzy situation that does not have big spherulite to cause.
Goods of the present invention also can be prepared as has multilayer, and wherein one deck is a polymer blend of the present invention, obtains by sheet material lamination or sheet material coextrusion.
Test procedure
Limiting viscosity (IV) according to ASTM D4603-03 test pill.
In closed reaction vessel under 220 ± 5 ℃ with the aqueous solution of polymkeric substance at ammonium hydroxide in the about content (weight %) of measuring glycol ether (DEG) in 2 hours of hydrolysis.Use the liquid portion of gas chromatographic analysis hydrolysate then.Gas chromatograph be available from the FIDDetector of Hewlett Packard (HP5890, HP7673A).Ammonium hydroxide is the SILVER REAGENT ammonium hydroxide available from the 28-30 weight % of Fisher Scientific.
The sample dissolution of polymkeric substance in the phenylcarbinol of SILVER REAGENT, and is measured carboxyl terminal (CEG) value of polymkeric substance with sodium hydroxide/benzyl alcohol solution titration to the purple end points of phenolsulfonphthalein telltale of 0.03N.The result represents with every kilogram of sample of mmole sodium hydroxide (mmol/kg).
According to ASTM D 648-01, method A measures heat-drawn wire (HDT) under the pressure of 0.455Mpa.The long 127mm of sample, wide 13mm, dark 13mm.
Use DMA Q800 instrument (TA Instruments, New Castle, Delaware, USA) by measure sample (film, long 15mm, wide 13mm, thick 0.5mm) temperature of the distortion under the stress (0.121%) that causes corresponding to the ASTM load by 0.455Mpa writes down deformation under load temperature (DTUL).Heating rate is 2 ℃/minute.
Use DMA Q800 instrument (TA Instruments, New Castle, Delaware, USA) on film sample with 2 ℃/minute heating rate and the frequency measurement storage modulus of 10Hz.
According to ASTM D638-03 type of service I sample determination tensile property.
Using GA to measure Gardner (Gardner) for how much according to ASTM D5420-04 impacts.
(MOCON Minneapolis MN) measures the oxygen flux of membrane sample under 0% relative humidity, 1 normal atmosphere and 25 ℃ to use Mocon Ox-Tran type 2/20.The mixture of 98% nitrogen and 2% hydrogen is as carrier gas, and 100% oxygen is as test gas.Before test, sample is regulated at least 24 hours with the oxygen in the atmosphere of removing trace in cell under nitrogen.Continue to regulate up to obtaining stable baseline, wherein oxygen flux changed less than 1% in 30 minutes cycle.Subsequently, oxygen is incorporated in the test cell.When oxygen flux changes end of test (EOT) less than 1% time in 30 minutes test period.Calculate oxygen permeability according to literature method about the permeability coefficient (from second diffusion law that has suitable final condition of Fick) of PET multipolymer.Document is as follows: Sekelik etc., Journal of Polymer Science Part B:PolymerPhysics, 1999, the 37 volumes, 847-857 page or leaf.Second document is Qureshi etc., Journal ofPolymer Science Part B:Polymer Physics, 2000, the 38 volumes, 1679-1686 page or leaf.The 3rd document is Polyakova etc., Journal of Polymer Science Part B:PolymerPhysics, 2001, the 39 volumes, 1889-1899 page or leaf.The unit of oxygen permeability is nmol/m.s.GPa.
Use differential scanning calorimeter (Perkin Elmer DSC-2, Norwalk, Connecticut, USA) relative crystallinity of mensuration polymkeric substance.The polymkeric substance of 10mg is heated to 300 ℃ with 10 ℃/minute, kept 2 minutes in this temperature, then with 10 ℃ of/minute coolings.Crystalline exotherm peak value (T when measuring cooling
Ch).
Embodiment 1
Use conventional DMT method to prepare polyester (PET), carry out SSP then, its various fillers that contain different concns are to obtain 0.85 final IV.The supplier of these fillers is as shown in table 1.
Table 1
Filler company
Lime carbonate Nyacol, Ashland, MA USA
Silicon-dioxide Nyacol, Ashland, MA USA
Mica Georgia Industrial Minerals, Sandersville, GA USA
Zinc oxide Bayer, Leverkusen, Germany
The polymer in-mold of filling is made the thick film of 0.5mm.Test membrane under metamict was annealed 1 hour at 150 ℃ in vacuum oven.30 ℃ of storage moduluss of measuring these films, the results are shown in Table 2.
Table 2
The sample storage modulus, MPa
The imperfect crystal formation shape
Contrast 531 1123
Lime carbonate, 3%, 0.4 μ m 495 1470
Lime carbonate, 3%, 1.2 μ m 650 1738
Lime carbonate, 3%, 2 μ m 681 1794
Silicon-dioxide, 2%, 0.1 μ m 620 1791
Zinc oxide, 2%, 35nm 427 undetermineds
Mica, 2%, 5 μ m 728 1373
Mica, 5%, 10 μ m undetermined 2001
Based on the storage modulus (stiffness) of annealing specimen, it has simulated hot formed annealing process, has prepared other samples of the selected filler of 1 weight % load.By these polymer manufacture samples, measure heat-drawn wire (HDT).The results are shown in table 3.
Table 3
Packing material size, μ m long-width ratio HDT, ℃
Contrast 142.0
Mica 0.5～2 143.8
Mica 10～30 164.2
Mica 18～60 165.9
Lime carbonate 2～1 162.6
When the micaceous particle diameter 30 the time, is observed the improvement of HDT greater than about greater than about 10 μ m, long-width ratio.
Embodiment 2
The polyester that contains the 10 μ m micas (long-width ratio～30) of 1 weight % according to the method preparation of embodiment 1.By amorphous polymer and in vacuum oven the polymer manufacture sample after 150 ℃ of annealing.Measure tensile property, the results are shown in table 4.
Table 4
Under the sample condition Young's modulus, overall loading
GPa tension force, %
Contrast amorphous 1.06 8.4
Mica, 1% amorphous 1.26 6.7
Contrast annealed 1.27 14.4
Mica, 1% annealed 1.40 15.9
In amorphous and annealed mica sample, all observe the improvement of Young's modulus.
Embodiment 3
Use three 10 μ m micaceous vibrin that contain 2.1 weight % of DMT method preparation.Prepare sample A (initial charge DMT, ethylene glycol and EI catalyzer) by when transesterify (IE) begins, adding mica slurry (30 weight % in EG).Prepare sample B by after EI, before the polymerization, adding mica slurry (30 weight % in EG).With the identical sample C for preparing of order of sample B, but in the mica slurry, also be incorporated as the sodium acetate of 0.1 weight % of initial charge weight.With the identical sample D for preparing of order of sample A, but in the mica slurry, also be incorporated as the sodium acetate of 0.1 weight % of initial charge weight.Measure the chemical property of these polymkeric substance, do not compare, the results are shown in table 5 with there being the micaceous contrast.
Table 5
Sample IV, dl/g DEG, weight % CEG, mmol/kg
Contrast 0.55 0.7 23
A 0.55 1.4 39
B 0.55 3.8 89
C 0.56 0.5 21
D 0.61 0.8 18
Add mica and obtain high DEG (sample B) after EI, its fusing point and HDT reduce and CEG improves.When EI begins, add mica and reduced DEG and CEG (sample A), but DEG and CEG value still are higher than contrast.Think that this increase is because the remaining acid in the mica causes.Adding buffer reagent (sample C and D) in mica belongs to normally DEG and CEG value.
Embodiment 4
Relatively impact with the Gardner with the different micaceous polymkeric substance of unequally loaded of (compounding) preparation that is mixed by melt polymerization/solid state polymerization path (MP/SSP).Use the 0.89IV comparison polymer by adding mica in forcing machine throat drying, (New Jersey USA) is mixed for American Leistritz, Summerville with the ZSE-GL twin screw extruder.Sheet is molded and spend the night 150 ℃ of crystallizations.The results are shown in table 6.
Table 6
| Mica, μ m | Mica, weight % | Method | IV | Average energy of rupture, J |
| Contrast 10 10 20 contrasts 10 10 20 | 0 2.1 5.0 5.0 0 2.1 5.0 5.0 | MP/SSP MP/SSP MP/SSP MP/SSP is mixed | 0.79 0.78 0.74 0.86 0.63 0.64 0.62 0.61 | 1.47 1.41 1.08 1.33 0.99 1.11 1.12 0.99 |
Loss during the Gardner impacts may be since when being mixed the loss of IV cause.
Successfully prepared and contained the masterbatch of 20 weight % micaceous polymkeric substance at the most.Because observing is mixed IV loss there is remarkable influence like this, therefore it is not tested.
Embodiment 5
The polymer molding film forming that contains 5 weight % micas (10 and 20 μ m) that will in embodiment 4, prepare by MP/SSP.These films are annealed the different times at 160 ℃ in stove.On these films, measure DTUL, the results are shown in table 7.
Table 7
Time, divide DTUL, ℃
Contrast 10 μ m micas, 20 μ m micas
(long-width ratio～30) (long-width ratio～60)
30 104 105 117
60 110 118 123
90 114 130 139
These results show the advantage by the molded annealing goods of larger-diameter mica particles (than the aspect ratio).
Embodiment 6
Prepare the film that thickness is 0.4-0.5mm by the polyester that contains unequally loaded different-grain diameter mica particles.These films were 160 ℃ of annealing 1 hour.Measure oxygen permeability, the results are shown in table 8.
Table 8
| Mica, μ m | Mica, weight % | Oxygen permeability, nmol/m.s.GPa |
| Contrast | 0 | 11.8 |
| 10 (long-width ratio～30) | 5 | 8.70 |
| 20 (long-width ratio～60) | 5 | 7.82 |
| 10 (long-width ratio～30) | 10 | 6.12 |
These results show that these mica particles have reduced the oxygen permeability of these films significantly, better to long-width ratio bigger under the fixed load.
Embodiment 7
Mensuration contains the crystallization rate of polymkeric substance of the 10 μ m micas (long-width ratio～30) of 1.0 and 2.1 weight %, the results are shown in table 9.
Table 9
Mica, weight % T
Ch, ℃
0 182.1
1 191.6
2 207.9
Although this embodiment is outside desired scope, it shows higher T when increasing mica content
ChShow crystallization rate faster.This faster speed be the annealed assessed value of thermoforming food tray.
Therefore according to the present invention, it provides a kind of method that can satisfy above-mentioned purpose, target and advantage fully.Although describe the present invention according to its specific implementations, clearly many to substitute, improve and change according to foregoing description be clearly for those skilled in the art.Therefore, it trends towards comprising that interior all of spirit and scope that fall into claim substitute, improve and change.
Claims (25)
1. polyester and resin composition that is used for articles thermoformed therefrom, it contains: comprise greater than 2 but less than the micaceous polyester of 10 weight %.
2. polyester and resin composition according to claim 1, it further contains impact modifying agent, nucleator and pigment that concentration is about 5 weight %-20 weight % of total composition.
3. polyester and resin composition according to claim 1, wherein said mica is in the scope of about 10-about 300 microns (μ m).
4. polyester and resin composition according to claim 4, wherein said mica is in the scope of the about 100 μ m of about 10-.
5. polyester and resin composition according to claim 1, wherein said mica have the long-width ratio greater than about 10.
6. polyester and resin composition according to claim 1, wherein said mica preferably have the long-width ratio greater than about 25.
7. polyester and resin composition according to claim 1, wherein said mica most preferably have the long-width ratio greater than about 50.
8. polyester and resin composition according to claim 1, it further contains the sodium acetate of the about 0.2 weight % of about 0.05-of promising described composition.
9. according to the described polyester and resin composition of claim 1-8, wherein said polyester contains 85 moles of % or higher polyethylene terephthalate.
10. a method for preparing polyester and resin composition comprises mica and polyester is mixed when esterif iotacation step begins.
11. a method for preparing polyester and resin composition comprises mica and polyester is mixed when esterif iotacation step finishes.
12. the method for preparing polyester and resin composition according to claim 10, wherein said mica is with concentration pulp in ethylene glycol of 30-40 weight %.
13. the method for preparing polyester and resin composition according to claim 10, it further is incorporated as the sodium acetate of the about 0.2 weight % of about 0.05-of described composition in mixing step.
14. the method for preparing polyester and resin composition according to claim 10, wherein said mica is in the scope of about 10-about 300 microns (μ m).
15. the method for preparing polyester and resin composition according to claim 10, wherein said mica have the long-width ratio greater than about 10.
16. the method for preparing polyester and resin composition according to claim 10, wherein said mica most preferably have the long-width ratio greater than about 50.
17. the method for preparing polyester and resin composition according to claim 10, it further contains the sodium acetate of the about 0.2 weight % of about 0.05-of promising described composition.
18. the method for preparing polyester and resin composition according to claim 10, it further contains impact modifying agent, nucleator and pigment that concentration is about 5 weight %-20 weight % of total composition.
19. the method for preparing polyester and resin composition according to claim 11, wherein said mica is in the scope of about 10-about 300 microns (μ m).
20. the method for preparing polyester and resin composition according to claim 11, wherein said mica have the long-width ratio greater than about 10.
21. according to the described method for preparing polyester and resin composition of claim 10-20, wherein said polyester contains 85 moles of % or higher polyethylene terephthalate.
22. the thermoformable goods by polyester and resin composition preparation, it contains and comprises greater than 2 but less than the micaceous polyester of 10 weight %, and described mica and has and is higher than about 10 long-width ratio in the scope of about 10-about 300 microns (μ m).
23. thermoformable goods according to claim 22, it contains the sodium acetate of the about 0.2 weight % of about 0.05-of promising described composition.
24. thermoformable goods according to claim 23, it further contains impact modifying agent, nucleator and pigment that concentration is about 5 weight %-20 weight % of total composition.
25. according to the described thermoformable goods of claim 22-24, wherein said polyester contains 85 moles of % or higher polyethylene terephthalate.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US2005/007541 WO2006096175A1 (en) | 2005-03-08 | 2005-03-08 | Polyester compositions having high dimensional stability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101155873A true CN101155873A (en) | 2008-04-02 |
Family
ID=36953677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800489712A Pending CN101155873A (en) | 2005-03-08 | 2005-03-08 | Polyester composition with high dimensional stability |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20080248285A1 (en) |
| EP (1) | EP1856204A4 (en) |
| CN (1) | CN101155873A (en) |
| BR (1) | BRPI0520042A2 (en) |
| CA (1) | CA2600267A1 (en) |
| MX (1) | MX2007010817A (en) |
| WO (1) | WO2006096175A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2476029A (en) * | 2009-11-06 | 2011-06-15 | Pregis Rigid Packaging Ltd | Polyethylene terephthalate copolymer container manufactured using nucleating agent |
| JP5587230B2 (en) * | 2011-03-25 | 2014-09-10 | 富士フイルム株式会社 | SOLAR CELL BACK SHEET, MANUFACTURING METHOD THEREOF, AND SOLAR CELL MODULE |
| JP7113595B2 (en) * | 2014-03-11 | 2022-08-05 | フラニックス・テクノロジーズ・ベーフェー | Polyester and method for preparing polyester |
| US20170335054A1 (en) * | 2014-11-21 | 2017-11-23 | Ester Industries Limited | Heat resistant polyethylene terephthalate and process of manufacturing thereof |
| CN109679302B (en) * | 2018-12-19 | 2021-01-12 | 中广核俊尔新材料有限公司 | High-modulus water-washing-resistant PBT zipper material and application thereof |
| CN112321950B (en) * | 2020-10-28 | 2022-12-20 | 中国石油化工股份有限公司 | High-impact polypropylene material and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4078143A (en) * | 1976-01-09 | 1978-03-07 | E. I. Du Pont De Nemours And Company | Process for depolymerizing waste ethylene terephthalate polyester |
| US4283326A (en) * | 1977-07-11 | 1981-08-11 | Gaf Corporation | PBT Molding compositions containing mica and a composite polymer |
| US4536425A (en) * | 1984-06-08 | 1985-08-20 | Continental Can Company | Method for preparing polar thermoplastic resin compositions having improved gas barrier properties |
| US6077904A (en) * | 1992-02-03 | 2000-06-20 | Lawson Mardon Thermaplate Corporation | Elevated temperature dimensionally stable, impact modified polyester with low gas permeability |
| JP3002394B2 (en) * | 1994-10-31 | 2000-01-24 | 出光石油化学株式会社 | Polycarbonate resin composition and automotive exterior member using the same |
| US5856424A (en) * | 1996-10-16 | 1999-01-05 | Eastman Chemical Company | Process for making polyesters containing low concentrations of diethylene glycol |
| US6020414A (en) * | 1996-10-23 | 2000-02-01 | Hoechst Celanese Corporation | Method and compositions for toughening polyester resins |
| US6084019A (en) * | 1996-12-31 | 2000-07-04 | Eastman Chemical Corporation | High I.V. polyester compositions containing platelet particles |
| JP2000143957A (en) * | 1998-07-14 | 2000-05-26 | Unitika Ltd | Polyester resin sheet for ic card and laminate and ic card using the same |
| US6576309B2 (en) * | 1999-12-02 | 2003-06-10 | Associated Packaging Enterprises | Thermoplastic compositions having high dimensional stability |
| CN1307259C (en) * | 2001-08-03 | 2007-03-28 | 东丽株式会社 | Resin composition and molding, film and fiber each comprising the same |
| JP2006525412A (en) * | 2003-05-02 | 2006-11-09 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | POLYESTER CONTAINING MICROFIBER AND METHOD FOR PRODUCTION AND USE THEREOF |
-
2005
- 2005-03-08 BR BRPI0520042-3A patent/BRPI0520042A2/en not_active IP Right Cessation
- 2005-03-08 MX MX2007010817A patent/MX2007010817A/en unknown
- 2005-03-08 WO PCT/US2005/007541 patent/WO2006096175A1/en active Application Filing
- 2005-03-08 CA CA002600267A patent/CA2600267A1/en not_active Abandoned
- 2005-03-08 US US11/817,709 patent/US20080248285A1/en not_active Abandoned
- 2005-03-08 EP EP05724962A patent/EP1856204A4/en not_active Withdrawn
- 2005-03-08 CN CNA2005800489712A patent/CN101155873A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2006096175A1 (en) | 2006-09-14 |
| BRPI0520042A2 (en) | 2009-04-14 |
| EP1856204A1 (en) | 2007-11-21 |
| CA2600267A1 (en) | 2006-09-14 |
| EP1856204A4 (en) | 2008-06-18 |
| US20080248285A1 (en) | 2008-10-09 |
| MX2007010817A (en) | 2007-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5258233A (en) | Polyester/polyamide blend having improved flavor retaining property and clarity | |
| EP0879265B1 (en) | Polyester/polyesteramide blends | |
| RU2450035C2 (en) | Method of producing copolyester polymers for transparent single-layer containers, demonstrating improved gas-permeability characteristics | |
| US5266413A (en) | Copolyester/polyamide blend having improved flavor retaining property and clarity | |
| US20100113626A1 (en) | Opaque containers containing colored recycled polyester | |
| AU2015257900B2 (en) | Injection-moulded article | |
| US20030032737A1 (en) | Polyester compositions of low residual aldehyde content | |
| JP2008523217A (en) | Mixing of oxygen-removing polyamide with polyester containing zinc and cobalt | |
| CA2948416C (en) | Articles produced by thermoforming | |
| NZ212508A (en) | Fusion blend of pet and a second polyester; articles prepared therefrom | |
| KR101156384B1 (en) | Injection-molded object | |
| CN101155873A (en) | Polyester composition with high dimensional stability | |
| CA2376152C (en) | Polyester compositions of low residual aldehyde content | |
| CN101362851A (en) | A polyester gas barrier resin and a process thereof | |
| EP2003169B1 (en) | Polyester resin composition, method for producing same and molded body | |
| JP5297912B2 (en) | Cellulose fiber reinforced polybutylene terephthalate resin composition | |
| TW201326300A (en) | Blend of polylactic acid resin and copolyester resin and articles using the same | |
| JP3662563B2 (en) | Method for producing saturated polyester composition for plastic containers having excellent heat resistance and gas barrier properties | |
| KR20070118600A (en) | Polyester compositions having high dimensional stability | |
| JP3059819B2 (en) | Polyester thermoformed product | |
| JPWO2006062148A1 (en) | POLYESTER RESIN, POLYESTER MOLDED ARTICLE COMPRISING THE SAME AND PROCESS FOR PRODUCING THE SAME | |
| JP2007138159A (en) | Polyester molded article and polyester stretch blow molded article | |
| JP2006188676A (en) | Polyester composition and polyester molded product composed of the same | |
| JPH02276855A (en) | Polyester resin composition and use thereof | |
| JPH06107817A (en) | Resin material for producing thermoformable sheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080402 |